Olefin oxide ortho ester condensation products



OLEFIN OXIDE ORTHO ESTER CONDENSATION PRODUCTS Otis C. Dermer, Stillwater, Okla., and Frank Bier Slezak, Painesville, Ohio, assignors to Cities Service Research and Development Company, New York, N. Y., a cor.- poration of New Jersey 7.

No Drawing. Application May 29, 1958 Serial No. 738,642

15 Claims. (Cl. 260-615) This invention relates, to novel organic compounds, and more. particularly to addition compounds of olefin oxides with orthoformates.

This application isa continuation-in-part of our copending application Serial No. 369,728, filed July 22, Y

1953, and now abandoned.

We have discovered that olefin oxides, such as ethylene oxide and propylene oxide, may be reacted with orthoformates, such as ethyl orthoformate, in the cold and in the presence of boron trifiuoride as a catalyst to produce adducts having the generic formula I-IC(OC H (OCH CH OC H Diethyl 2-ethoxyethyl orthoformate The 2 oxide: 1 orthoester adducts HC(C H (OCH CH OCH CH OC H Diethyl 2-(2-ethoxyethoxy)ethyl orthoformate HC(OC H (OCH CH OC H Ethoxy-bis-(2-ethoxyethoxy)methane Ethyl biS-Z-ethoxyethyl orthoformate The3 oxidezl orthoester adducts Rowena),

(OCH CH OCH CH 0CH CH OC H (IV) Diethyl 2-(2-(2-ethoxyethoxy) ethoxy) ethyl orthoformate C2 5) (OCH2CH2OC2H5) (OCH CH OCH CH OC H (V) ethyl 2-ethoxyethyl 2-(2-ethoxyethoxy) ethyl orthoformate HC(OCH CH OC H (VI) Tris-(2-ethoxyethoxy)methane M Tris-2-ethoxyethyl orthoformate It is believed that propylene oxide and ethyl ortho- (III) formate give the same types of isomers as noted above.

' However, they introduce new possibilities of isomerism were determined by standard microanalytic al techniques,-

2,867,667 Patented Jan. 6,

2 because of thefact that the propylene oxide ring can open in either of two ways. It can be shown that there must be 2 isomers corresponding to I, 4 to'II, 3 to III, 8 to IV, 6 to V, and 4 to VI.

We have found that the reaction will proceed smoothly at temperatures in the neighborhood of 0 C. or. below, in the presence of 0.5% or less of boron trifluorlde. 'Even at room temperature the catalyst degrades and destroys the orthoformatequite rapidly, so that it is essential to maintain low temperatures during the reaction; Catalyst concentrations higher than 0.5% are'uns'atisfactory, leading to decomposition of the ortho-formate, and aQconsequent lowering of the yield of the desired products. Boron fluoride is the only substance known to us to catalyze the reaction, since attemptsto condense ethyl Orthoformme with ethylene oxide by means of suL- furic acid or stannic chloride catalyst at or below room temperature gave only the recovered ester and its hydrolysis products. The same reagents gave the same results when the catalyst used was hydrated calcium silicate. -Attempted uncatalyzed thermal condensation of the oxide and the orthoester also gave no reaction. In order to illustrate our invention more clearly, the following examples are given:

EXAMPLE 1 (a) Preparative data Boron trifluoride (1.5 g., 0.02 mole) was dissolved in 300 g. (2 moles) ethyl orthoformate. This solution was added to a one-liter, three-necked flask equipped with an ice-water-cooled reflux condenser, a power stirrer, and a thermometer. The reaction flask was immersed in an ice bath.

Ethylene oxide (22 g., 0.5 mole) was dissolved in g. (1 mole) of chilled ethyl orthoformate. This mixture was added with stirring to the catalyst solution at such a rate as to maintain the reaction temperature between 3 and 6 C. Forty-five minutes were required for the addition. The reaction mixture was then stirred at ice-bath temperature for an additional five hours.

Anhydrous potassium carbonate (25 g.) in about 30 ml. of water was added to neutralize the boron trifiuoride. The solution became somewhat milky as the neutralization took place. Stirring was continued an additional thirty minutes and then 50 g. of anhydrous sodium sulfate was stirred into the mixture. After fifteen minutes, the stirrer was shut off and the mixture allowed to warm to room temperature overnight.

The solids were filtered off and washedwith ethyl ether, the ether washings were combined with the filtrate, and the mixture was distilled at atmospheric pressure to remove the ethyl ether, ethyl orthoformate decomposition products and finally the excess ethyl orthoformate. The residue was then distilled at reduced pressure on a Todd column to separate the products.

About 45 g. of material corresponding to I (1 oxide: "1 orthoester adduct) was obtained boiling-at 1'12-117 C./35 mm. Ten grams of material corresponding to II and III (2 oxide: 1 orthoester adduct isomers) was obtained boiling at 156-158 C./35 mm.

Another reaction using a lower ratio of orthoester'to ethylene oxide also yielded some material corresponding to IV, V and VI (3 oxide: 1 orthoester adduct isomers) boiling at 149-158 C./l mm. or 184187 C./36 mm.

(b) Analytical data Thecarbon and hydrogen values of the above products (c) Physical constants The boiling ranges tabulated below were determined during the analytical distillationsof the reaction mixtures. The refractive indices were determined by means of an Abbe-type refractometer with prisms maintained at 20 C. The specific gravity was determined by the use of a 1 ml. pycnometer and referred to water at 20 C. The molar refractions were calculated by means of the L- rentz-Lorenz equation using the theoretical molecular weight of the compound in conjunction with the experimentally derived refractive index and density. The theoretical molar refraction was obtained from the sum of the-atomic refractions for the postulated structures.

1 OXIDE: 1 ORTHOESTER ADDUCT (I) Boiling range 115-117 C./36 mm. Refractive index C. 1.4060 Specific gravity, 20/20 0.9270 Density, 20,'g'./ml. 0.9254 Experimental molar refraction 51.02 Theoretical molar refraction 50.33

2 OXIDE 1 ORTHOESTER ADDUCT ISOMERS (II AND 111) Boiling range 157-159 C./36' mm. Refractive index, 20 C. 1.4190 Specific gravity, 20/20 0.9842 Density, 20, g./ml. 0.9824 Experimental molar refraction 60.62 Theoretical molar refraction 60.21

3 OXIDE: 1 ORTHOESTER ADDUCT' ISOMERS (IV, V, AND VI) Boiling range 184-187 C./'36- mm. Refractive index, 20 C. 1.4208 Specific gravity, 20/20 0.9905 Density, 20"., g./ml. 0.9887 Experimental molar refraction 71.85 Theoretical molar refraction 72.09

((1) Proof of structure ether washings were combined with the organic layer for distillatiorron 2. Todd column.

Distillation of the hydrolysis products from the 1 ethylene oxide: 1 ethyl orthoformate adduct yielded ethanol and 2-ethoxyethanol. The latter was identified by the formation of the 3,5-dinitrobenzoate. The derivative melted at 67-69" C. A mixture of the above derivative with the 3,5-dinitrobenzoate of a known sample of 2- ethoxyethanol melted at 6870 C.

The fact that no products other than ethanol and 2- ethoxyethanol were found as alcohols shows that the 1:1 compound is I.

Distillation of the hydrolysis products from the 2 ethylene oxide: 1 ethyl or-tho formate' adduct isomer mixture yielded ethanol, 2-ethoxyethanol, and somematerial of B; P. 185-195 believed to be 2-(2-ethoxyethoxy)ethanol (literature B. P., 202). The 2-e'thoxyethanol was again identified by the formation of the 3,5-dinitrobenzoate. No satisfactory derivative of the higher-boiling material could be obtained. About four times as much 2- ethoxyethanol as the higher-boiling material was obtained. The only other material which might be present and which would have a boiling range in the regionobserved for the high-boiling material would beethylene glycol. The product received was found to be miscible with petroleum ether whereas ethylene" glycol was found to be' insoluble. Thus the high-boiling material is in all probability 2-(2-ethoxyethoxy) ethanol.

From the hydroly sis'fragments received, it follows that the 2:1 product is an isomeric mixture of II and III.

Distillation of the hydrolysis products from the 3 ethylene oxide: 1 ethyl orthoformate adduct isomers yielded ethanol, Z-ethoxye'thanol, 2 (2-ethoxyethoxy)ethanol and some still higher-boiling material believed to be 2-(2-(2-ethoxyethoxy)ethoxy)ethanol. The 2-ethoxyethanol was again identified as the 3,5-dinitrobenzoate. Again no derivative of the 2-(2-ethoxyethoxy)ethanol could be obtained. It was assumed to be the'materialstated on the basis of boiling range (194-197" C.) solubility in water and petroleum ether, and refractive index.

Observed l Literature at 20 at26 1. 4238' r refractive index of different samples. 1. 4244 Since only a small amount (1-2 ml.) of material boiling above 197 C. was obtained, n'o identification of the material could be made. It is however likely'to have been 2-(2-(2-ethoxyethoxy)ethoxy)ethanol.

Onthe basis of the hydrolysis fragments obtained, it readily follows that the 3 1 adduct is an isomeric mixture of IV, V, and VI.

EXAMPLE 2 (a) Preparative data Boron trifiuoride (1.5- g., 0.02 mole) was dissolved in 300 g. (2 moles) of ethyl orthoforrnate. This solution was added to a one-liter three-necked flask equipped with an ice-water-cooledreflux condenser, a power stirrer and a thermometer. The reaction flask was immersed in an ice bath.

Propyleneoxide (30 g., 0.5 n'1ol'e was dissolved in g. (1 mole) of chilled ethyl ortho'formate. This solution was addedwith stirringto the catalyst solution" at such a rate as to maintain the reaction temperature between 3 and 8 C. About an' hour was required for the addition. The reaction mixture wasthen stirred at ice-bath temperature for an additional seven hours.

Anhydrous potassium carbonate (30 g.) in about 30 ml. of water was-added to neutralize the boron trifluoride. Stirring was continued twenty minutes-and then 50 g; of anhydrous sodium sulfate was added. After thirty min'utes the stirrer was shutoff and" the mixture allowed t'owarm to room temperature overnight;

apex-ear The:.solidswere filtered'off and washed-with ether.- The .ether washings were combinedwith the filtrate and the mixture distilled at atmospheric pressure to remove the ethyl ether, ethyl orthoformate decomposition prodnets and finally the excess ethyl orthoformate. The residue was then distilled at reduced pressure in a Todd column'to separate, the products.

A 37% yield, based on propylene oxide, of the 1 oxidezl orthoester adduct isomers was obtained boiling at 113-119" C./36 mm. A 20% yield of the 2 oxidezl orthoester adduct isomers was obtained boiling at 151- 153 C./36 mm. An 11% yield of 3 oxidezl orthoester adduct isomers was obtained boiling at 172-179 C./36

(b) Analytical data The carbon and hydrogen values of the above products .were determined as before by standard microanalytical techniques '1 PROPYLENE OXIDE: 1 E'IHYL ORTHOFORMATE ADDUCT ISOME-RS Calculated for Experimental 010E220; Average Percent C 3 58.22 57.99 Percent H 10. 75 11.12

2 PROPYLENE OXIDE :lETBYL ORTHOFORMATE ADDUCI ISOMERS Calculated for Experimental CraHaaOs Average Percent C 59. 58. 40 Percent H 10. 67 10. 71 v 3 PROPYLENE OXIDE: 1 ETHYL ORTHOFORMATE ADDUC'I ISOMERS Calculated for Experimental CmHuOe Average Percent C 59. 59 59. 71 fer-cent H 10.62 10. 94

(c) Physical constants The same procedures were used as for the determination of the physical constants of the ethylene oxide-ethyl orthoformate adducts.

1 PROPYLENE OXIDE: 1 ETHYL ORTHOFORMATE ADDUCT ISOMERS Boiling range 113-119" C./36 mm. Refractive index, C 1.4040 Density, 20, g./m1 1.9123 Experimental molar refraction 55.28 Theoretical molar refraction 54.95

' 2 PRCPYLENECXIDE: 1 ETHYL ORTHOFORMATE ADDUC'J. ISOMERS (d) Proof of structure No attempt was made to prove-the structure of these compounds on account of .the' large variety of isomers that would undoubtedly result from the hydrolysis of the adducts. I The structure of these compounds must follow by analogy to the ethylene oxide-ethyl orthoformate adducts. v

In a manner similar to that set forth in the foregoing examples, other orthoformates may be reacted with ethylene oxide or propylene oxide. Typical orthoformates suitable for this purpose are methyl orthoformate, propyl orthoformate, butyl orthoformate and amyl orthoformate. The examples which follow are typical of the preparation of condensation products with the foregoing compounds.

' i I EXAMPLE! Boron trifluoride (1.5 g., 0.02 mole) was passed into methyl orthoformate (106 g., lrnole) at 0. The'resulting solution was transferred to a oneiliter three neck flask equipped with an eflicient power stirrer, a therm:

ometer, and an ice-water 'cooled reflux condenser. The

reaction flask was immersed in an ice bath. An additional 106 g. (1 mole) of chilled methyl orthoformate were used to rinse the catalyst solution into the reaction flask.

Ethylene oxide (50 ml., 1 mole) and methyl orthoformate 106 g., 1 mole) at 0 were mixed and the re sulting solution added to the catalyst solution, with stirring, over a 1.5-hour period. The temperature of the reaction mixture was maintained between 3 and 5. After all the ethylene oxide solution had been added, the mixture was stirred at 0-5 an additional three hours and then was treated with 30 g. of anhydrous potassium carbonate in about 30 ml. of water. Over a 30-45 min ute period of stirring, the mixture change in color from 'a deep brown-red, through a wine color, to a yellow-.- orange solution. Anhydrous sodium sulfate (30-40 g.) was then added to the reaction mixture and stirring was continued an additional 30 minutes.

The solids were filtered off and washed with two 25-mlL portions of ethyl ether. The ether washings were combined with the organic filtrate and the mixture was dis"- tilled. After the ethyl ether, methyl orthoformate decomposition products, and excess methyl orthoformate were removed, 30 g. (20% yield) of dimethyl 2-meth oxyethyl orthoformate were obtained boiling at 172- 174/743 mm. The residue distilled with decomposition even at reduced pressure (20 mm.)

The physical properties of this dimethyl 2-methoxyethyl orthoformate are as follows: a

Boiling range 172-17 4/743 mm.

20 1.4012 2 1.001 Calc. mol. wt 150.2 Avg. exp. mol. wt 152 Calc. molar refraction 36.36 Exp. molar refraction 36.47 Percent C:

Calc. 47.99 Exp. 48.09

Percent H: 'Calc. 9.39 Exp. 9.41

EXAMPLE 4 reaction flask. Ethylene oxide (1 mole) and 'butyl orthoformat'e,(-1 -mole)- at zero degrees are mixed and the re:-

7 sulting" solution added to the catalystsolution with stir ringover a period of approximately twohours. The temperature of the" reaction mixture is maintained at between about 3 and 6 C.

After all the ethylene oxide solution is added, the mixture is' stirred an additional three hours and treated with approximately 30 grams of anhydrous potassium carbonate in about 30 ml. of water. The mixture is again stirred for a short period of time, after which from 30 to 50 grams of anhydrous sodium sulfate is added to the reaction mixture and stirring continued an additional 30 minutes.

The solids are then filtered OE and washed with ether with the mixture being distilled to remove decompositiori products and excess butyl orthoformate. The final reaction product is then recovered.

The products of this invention may be used for a variety of purposes. The unique properties of these olefin oxide orthoester condensation products make them particularly suitable as solvents. For example, the adduct isomers of the present invention may be used in preparing solvent cutback rust preventives similar to the manner in which Stoddard solvent is now used. Blends have been made using the product of Example 1 as a cutback solvent with petrolatum, black wax (M. P. 190-195' F.), and microcrystalline wax. The products are suitable as low temperature dewaxing solvents and also as asphalt extractants.

In addition to their use as solvents, the new compounds of the present invention may be utilized as plasticizers. To demonstrate their suitability for this purpose, two solutions were prepared with Lucite powder (methacrylate polymer M. P. 300 F.-Buehler transoptic molding powder-clear). The first solution contained the Lucite powder dissolved in methylethyl ketone. The second solution contained in addition to the Lucite powder and methylethyl ketone, a small amount of the product of Example 1. These solutions were placed on glass plates and heated gently to remove the solvent and set the plastic. The sample prepared without the adduct product of Example 1 was hard and brittle, whereas the sample containing the product of Example 1 formed a flexible clear skin-like film.

While we have described our invention with some degree of particularity, it is to be understood that we intend to limit our invention only by the claims appended hereto.

We claim: 4 1. A compound having the generic formula HO(OA)'OR (OALwOR in which A is a bivalent hydrocarbon radical selected from the group consisting of ethylene and propylene; n is an integer from 1 to 4 inclusive; n' and n" are any integers from 0 to 4 inclusive and R is an alkyl group 'having from 1 to 5 carbon atoms.

in which A is a bivalent hydrocarbon radical selected from the group consisting of ethylene and propylene; n

8 is an integer from" 1- to 4 inclusive; nv and n" arelany' integersfrom 0 to 4"inc-lusive and R is an alkyl group having from 1 to 5 carbon atoms, which comprises ree acting an olefin: oxide selected from the group consisting of ethylene and propylene with an alkyl orthoformate in the presence of not more than 0.5% of boron trifluoride at a temperature between about 0 C. and 10 C.

8. A process for preparing organic compounds having the generic formula (OA'MOR HC-(OA),.'OR

(O'A')1|"OR in which A is a bivalent hydrocarbon radical selected from the group consistingv of ethylene and propylene; n is an integer from 1 to 4 inclusive; n and n" are any integers from 0 to 4 inclusive and R is an alkyl group having from 1 to 5 carbon atoms, which comprises reacting one molar proportion of an olefin oxide selected from the group consisting of. ethylene and propylene with about six molar proportions of an alkyl orthoformate in the presence of not more than 0.5 of boron trifluoride at a temperature maintained between about 0 C. and 10 C.

9. A process for preparing organic compounds having the generic formula no-(omuon (OA)1|"0R in which A is a bivalent hydrocarbon radical selected from the group consisting of ethylene and propylene; n is an integer from 1 to 4 inclusive; n and n" are any integers from 0 to 4 inclusive and R is an alkyl group having from 1 to 5 carbon atoms, which comprises reacting an olefin oxide selected from the group consisting of ethylene and propylene with an alkyl orthoformate in the presence of less than 0.5% of boron trifluoride at a temperature between about 0 C. and 10 C. until the reaction is complete, adding a basic material to neutralize the boron trifluoride and distilling the resulting mixture to separate the reaction products.

10. A process for preparing organic compounds having the generic formula (0A)..-0R in which A is a bivalent ethylene radical; n is an integer from 1 to 4 inclusive; n and n" are any integers from 0 to 4 inclusive and R is an ethyl group, which comprises reacting about 3 molecular portions of ethyl orthoformate with about one half molecular proportion of ethylene oxide in the presence of about 0.02 mol of boron trifluoride at a temperature between about 3 C. and about 6 C.

11. A process for preparing organic compounds. having the generic formula ire-(019M011 (OALWQR in which A is, a bivalent ethylene radical; n is an integer from Ito 4 inclusive; n and n" are any integers from 0 to 4 inclusive and R is a methyl group, which comprises reacting about 3 molecular proportions of methyl orthoformate with about one half molecular proportion of ethylene oxide in the presence of about 0.02 mol of boron trifluoride at a temperature between about 3"" C. and about 6 C.

12. A process for preparing organic compounds having the generic formula (OAMOR HC-r-(OA1mOR (OAL OR 9 in which A is bivalent ethylene radical; n is an integer from 1 to 4 inclusive; n and n" are any integers from to 4 inclusive and R is a butyl group, which comprises reacting about 3 molecular proportions of butyl orthoin which A is a bivalent propylene radical; n is an integer from 1 to 4 inclusive; n and n" are any integers from 0 to 4 inclusive and R is an ethyl group, which comprises reacting about 3 molecular proportions of ethyl orthoformate with about one half molecular proportion of propylene oxide in the presence of about 0.2 mol of boron trifluoride at a temperature between about 3 C. and about 8 C.

14. A process for preparing organic compounds having the generic formula in which A is a bivalent propylene radical; n is an integer from 1 to 4 inclusive; n and n are any integers from 0 to 4 inclusive and R is a methyl group, which comprises reacting about 3 molecular proportions of methyl orthoformate with about one half molecular proportion of propylene oxide in the presence of about 0.2 mol of boron trifluoride at a temperature between about 3 C. and about 8 C.

15. A process for preparing organic compounds having the generic formula in which A is a bivalent propylene radical; n is an integer from 1 to 4 inclusive; n and n" are any integers from 0 to 4 inclusive and R is an ethyl group, which comprises reacting about 3 molecular proportions of ethyl orthoformate with about one half molecular proportion of propylene oxide in the presence of about 0.2 mol of boron trifluoride at a temperature between about 3 C. and about 8 C. until the reaction is complete, adding a basic material to neutralize the boron trifluoride and distilling the resulting mixture to separate the reaction products.

No references cited.

UNITED STATES PATENT ()FFICE Certificate of Correction Patent No. 2,867,667 January 6, 1959 Otis C. Dermer et a1.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, line 54, for 1.9123 read 0.9123; column 9, lines 11 to 14 inclusive, the formula should appear as shown below instead of as in the patent (OA),.OR

HG(OA)'OR (OA)||"OR Signed and sealed this 19th day of May 1959.

Attest': KARL H. AXLINE, ROBERT C. WATSON, Attesti/ng Qfiaer. Commissioner of Patents.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,867,667 January 6, 1959 Otis C. Dormer et a1.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, line 54, for 1.9123 read -O.9123-; column 9, lines 11 to 14: inclusive, the formula should appear as shown below instead of as in the patent (OA),.OR

BIO-(OALuOR (OA),.-OR

Signed and sealed this 19th day of May 1959.

Atbest: KARL H. AXLINE, ROBERT C. WATSON, Attesti/ng Qficer. I Oommz'ssz'oner of Patents. 

1. A COMPOUND HAVING THE GENERIC FORMULA
 7. A PROCESS FOR PREPARING ORGANIC COMPOUNDS HAVING THE GENERIC FORMULA 